CN107236991B - Large-size hexabasic rare earth boride single crystal cathode material and preparation method thereof - Google Patents

Large-size hexabasic rare earth boride single crystal cathode material and preparation method thereof Download PDF

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CN107236991B
CN107236991B CN201710441779.4A CN201710441779A CN107236991B CN 107236991 B CN107236991 B CN 107236991B CN 201710441779 A CN201710441779 A CN 201710441779A CN 107236991 B CN107236991 B CN 107236991B
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张久兴
宁舒羽
王盼
王衍
杨新宇
李志�
胡可
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Hefei University of Technology
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
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    • H01J1/02—Main electrodes
    • H01J1/13—Solid thermionic cathodes
    • H01J1/14—Solid thermionic cathodes characterised by the material
    • H01J1/148—Solid thermionic cathodes characterised by the material with compounds having metallic conductive properties, e.g. lanthanum boride, as an emissive material

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Abstract

The invention discloses a large-size hexabasic rare earth boride single crystal cathode material and a preparation method thereof, and the large-size hexabasic rare earth boride single crystal cathode material comprises (La)xCeyPrzNduGdv)B6Wherein x + y + z + u + v ═ 1, and is prepared by adopting a method combining spark plasma sintering and suspension zone melting. The hexabasic rare earth boride monocrystal prepared by the method has the characteristics of large size, high quality and higher current emission density.

Description

Large-size hexabasic rare earth boride single crystal cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of rare earth boride cathode materials, and particularly relates to a large-size hexabasic rare earth boride single crystal cathode material.
Background
Rare earth hexaboride (ReB)6Re is rare earth element) is a stable boride with a simple cubic structure, and the material has the advantages of low work function, high melting point, high hardness, good chemical stability, low evaporation rate and the like, and is an excellent hot cathode material. To date, the focus of research has been mainly on LaB6And CeB6And the like. Research shows that doping part of light rare earth elements, namely La, Ce, Pr, Nd, Gd and the like can effectively reduce the work function of the material and improve the electron emission performance of the material. Multicomponent rare earth borides such as LaxCe1-xB6、CexPr1-xB6、LaxNd1-xB6Etc. have higher electron emission properties than binary rare earth borides. Therefore, the hexabasic rare earth boride single crystal cathode material is prepared, the effect of reducing the work function of the material by integrating each light rare earth element is integrated, and the electron emission performance of the rare earth boride cathode material is expected to be comprehensively improved.
The rare earth hexaboride single crystal can be prepared by vapor deposition, aluminum flux, molten salt electrolysis and zone melting. The vapor deposition method has a defect that the adhesion between the thin film and the substrate is weak and the emission performance is directly affected. The aluminum flux method has the defects of long period and small size of the prepared single crystal, the length, the width and the height are generally within the range of 1-2 mm, and the existence of impurity aluminum in the crystal is difficult to avoid, so that the quality of the single crystal is influenced. The molten salt electrolysis method is easy to introduce impurities, resulting in low single crystal quality. Preparation of LaB by optical zone melting method6And CeB6The electron emission performance of the single crystal cathode material obtained by the binary rare earth boride is greatly improved compared with that of the previous methods. However, because the melting point of the rare earth boride with different compositions is different from the light absorption rate, compared with a binary rare earth boride single crystal, the multi-element rare earth boride single crystal has the problems that the components of each part are not uniform and the melting area is difficult to stabilize in the optical zone melting growth process, and has great influence on the quality of the single crystal. The rare earth boride single crystal material prepared by the optical zone melting method at present still has the defects of small size and low current emission performance. Therefore, the preparation technology of the rare earth hexaboride with large size (diameter larger than 6mm) and high performance needs to be explored.
Disclosure of Invention
The invention aims to explore the potential of electron emission performance of the polynary rare earth boride, integrate the effect of reducing work function of a cathode material by each light rare earth element, and provide a high-purity and large-size hexabasic rare earth boride single crystal cathode material and a preparation method thereof for meeting the requirements of a cathode device on larger size and higher electron emission of the material.
The composition of the large-size hexabasic rare earth boride single crystal cathode material of the invention is (La)xCeyPrzNduGdv)B6Wherein x + y + z + u + v ═ 1. The invention adopts a method of combining Spark Plasma Sintering (SPS) and suspension zone melting to prepare high-quality (La)xCeyPrzNduGdv)B6The method comprises the following steps:
(1) mixing LaB6、CeB6、PrB6、NdB6And GdB6The powder is mixed according to a molar ratio x: y: z: u: v, ball-milling and uniformly mixing, putting into a graphite mold, then putting the graphite mold into a cavity of a discharge plasma sintering furnace, sintering under the condition that the vacuum degree is not higher than 6Pa, and setting process parameters as follows: the sintering temperature is 1400-1850 ℃, the sintering pressure is 30-50 MPa, the heat preservation time is 5-15 min, and the heating rate is 60-200 ℃/min; cooling to room temperature along with the furnace after sintering is finished, and taking out to obtain a polycrystalline sample;
(2) cutting the polycrystalline sample into polycrystalline rods, respectively taking the two polycrystalline rods as a material rod and a seed crystal, adding the material rod and the seed crystal into an optical zone melting furnace for zone melting for the first time, and introducing high-purity argon into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are rotated reversely, the rotating speed is 15-30 rpm, and the crystal growth speed is controlled to be 10-40 mm/h;
(3) taking a product of primary zone melting as a material rod and LaB6The single crystal is used as seed crystal, added into an optical zone melting furnace for secondary zone melting, and high-purity argon is introduced into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are rotated reversely, the rotating speed is 15-30 rpm, and the crystal growth speed is controlled to be 1-20 mm/h; obtaining the large-size hexabasic rare earth boride single crystal cathode material after the secondary zone melting.
Compared with the prior art, the invention has the following beneficial effects:
the hexabasic rare earth boride (La) prepared by the inventionxCeyPrzNduGdv)B6The single crystal has the characteristics of large size and high quality; according to the obtained physical photo of the single crystal, the sample is a bluish purple cylindrical block with the diameter of 6-7 mm, and the surface is smooth; the Laue diffraction photo of the single crystal shows that diffraction spots are all independent spots and have no splitting phenomenon; the test result of the 360-degree X-ray single crystal diffractometer shows that the diffraction spots of the single crystal are clear, independent and not split, and the whole set of lattice is completely matched with the fitted lattice, which indicates that the single crystal has good quality; thermionic emission system testingThe results show that the current emission density of the sample is higher.
Drawings
FIG. 1 is (La) prepared in example 10.1Ce0.6Pr0.1Nd0.1Gd0.1)B6A physical photograph of the single crystal;
FIG. 2 is (La) prepared in example 10.1Ce0.6Pr0.1Nd0.1Gd0.1)B6A Laue diffraction photograph of a single crystal;
FIGS. 3(a) and (b) are respectively (La) prepared in example 10.1Ce0.6Pr0.1Nd0.1Gd0.1)B6Typical diffraction pattern and representativeness of single crystal 360 DEG X-ray diffraction of [100 ]]A diffraction pattern of directions;
FIG. 4 is (La) prepared in example 20.2Ce0.2Pr0.2Nd0.2Gd0.2)B6Current emission density of the single crystal.
Detailed Description
The present invention will be described with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. Any variations and modifications which do not alter the concept of the invention are within the scope of the invention.
The following examples used a spark plasma sintering furnace model of LABOX-350 and an optical zone furnace model of FZ-T-2000-X-I-VPO-PC.
Example 1
This example was prepared as follows (La)0.1Ce0.6Pr0.1Nd0.1Gd0.1)B6Single crystal:
(1) mixing LaB6、CeB6、PrB6、NdB6And GdB6Powder is prepared by mixing the following components in an atomic ratio of 1: 6: 1: 1: 1, ball-milling and uniformly mixing, putting into a graphite mold, then putting the graphite mold into a cavity of a discharge plasma sintering furnace, sintering under the condition that the vacuum degree is not higher than 6Pa, and setting technological parameters as follows: sintering temperature 1650 ℃ and sintering pressure40MPa, the heat preservation time is 5min, and the heating rate is 80 ℃/min; cooling to room temperature along with the furnace after sintering is finished, and taking out to obtain a polycrystalline sample;
(2) cutting a polycrystalline sample into polycrystalline rods with the diameter of 6mm, respectively taking the two polycrystalline rods as a material rod and a seed crystal, adding the polycrystalline rods into an optical zone melting furnace for zone melting for the first time, and introducing high-purity argon into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are reversely rotated, the rotating speed is 15rpm, and the crystal growth speed is controlled to be 20 mm/h;
(3) taking a product of primary zone melting as a material rod and LaB6The single crystal is used as seed crystal, added into an optical zone melting furnace for secondary zone melting, and high-purity argon is introduced into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are reversely rotated, the rotating speed is 15rpm, and the crystal growth speed is controlled to be 5 mm/h; obtained after the second zone melting (La)0.1Ce0.6Pr0.1Nd0.1Gd0.1)B6A single crystal.
FIG. 1 shows (La) obtained in this example0.1Ce0.6Pr0.1Nd0.1Gd0.1)B6The picture of the single crystal is a real picture, and the single crystal is smooth in surface, free from overflow trace of gas and impurities and blue-purple in color. The crystal diameter phi is 6mm, and the length is 28 mm. FIG. 2 is a Laue diffraction photograph in the growth direction, wherein the diffraction spots are all independent spots and have no splitting phenomenon, and the crystal is preliminarily judged to be a single crystal. FIGS. 3(a) and (b) are each (La)0.1Ce0.6Pr0.1Nd0.1Gd0.1)B6Typical diffraction pattern and representativeness of single crystal 360 DEG X-ray diffraction of [100 ]]The diffraction spots of the diffraction pattern in the direction are clear, independent and not split, the whole set of lattice is completely matched with the fitted lattice, and the single crystal is a cubic structure, so that the single crystal is determined to be high-quality.
Example 2
This example was prepared as follows (La)0.2Ce0.2Pr0.2Nd0.2Gd0.2)B6Single crystal:
(1) mixing LaB6、CeB6、PrB6、NdB6And GdB6Powder is prepared by mixing the following components in an atomic ratio of 1: 1: 1: 1: 1, ball-milling and uniformly mixing, putting into a graphite mold, then putting the graphite mold into a cavity of a discharge plasma sintering furnace, sintering under the condition that the vacuum degree is not higher than 6Pa, and setting technological parameters as follows: the sintering temperature is 1600 ℃, the sintering pressure is 40MPa, the heat preservation time is 5min, and the heating rate is 100 ℃/min; cooling to room temperature along with the furnace after sintering is finished, and taking out to obtain a polycrystalline sample;
(2) cutting a polycrystalline sample into polycrystalline rods with the diameter of 6mm, respectively taking the two polycrystalline rods as a material rod and a seed crystal, adding the polycrystalline rods into an optical zone melting furnace for zone melting for the first time, and introducing high-purity argon into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are reversely rotated, the rotating speed is 15rpm, and the crystal growth speed is controlled to be 20 mm/h;
(3) taking a product of primary zone melting as a material rod and LaB6The single crystal is used as seed crystal, added into an optical zone melting furnace for secondary zone melting, and high-purity argon is introduced into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are reversely rotated, the rotating speed is 15rpm, and the crystal growth speed is controlled to be 1 mm/h; obtained after the second zone melting (La)0.2Ce0.2Pr0.2Nd0.2Gd0.2)B6A single crystal.
Obtained in this example (La)0.2Ce0.2Pr0.2Nd0.2Gd0.2)B6The surface of the single crystal body is smooth, and no trace of gas and impurity overflow appears, which indicates that the crystal growth is uniform. The crystal diameter is about phi 6.5mm and the length is 25 mm.
From the analysis of the sample by Laue diffraction and single crystal X-ray diffraction, the sample obtained in this example was a high quality single crystal.
FIG. 4 shows the present example (La)0.2Ce0.2Pr0.2Nd0.2Gd0.2)B6The current emission density of the single crystal samples, which is seen to be higher, is indicative of a superior single crystal cathode material for the single crystal material.
Example 3
This example was prepared as follows (La)0.1Ce0.5Pr0.1Nd0.1Gd0.2)B6Single crystal:
(1) mixing LaB6、CeB6、PrB6、NdB6And GdB6Powder is prepared by mixing the following components in an atomic ratio of 1: 5: 1: 1: 2, ball milling and uniformly mixing, putting into a graphite mold, then putting the graphite mold into a cavity of a discharge plasma sintering furnace, sintering under the condition that the vacuum degree is not higher than 6Pa, and setting process parameters as follows: the sintering temperature is 1650 ℃, the sintering pressure is 40MPa, the heat preservation time is 5min, and the heating rate is 80 ℃/min; cooling to room temperature along with the furnace after sintering is finished, and taking out to obtain a polycrystalline sample;
(2) cutting a polycrystalline sample into polycrystalline rods with the diameter of 6mm, respectively taking the two polycrystalline rods as a material rod and a seed crystal, adding the polycrystalline rods into an optical zone melting furnace for zone melting for the first time, and introducing high-purity argon into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are reversely rotated, the rotating speed is 15rpm, and the crystal growth speed is controlled to be 20 mm/h;
(3) taking a product of primary zone melting as a material rod and LaB6The single crystal is used as seed crystal, added into an optical zone melting furnace for secondary zone melting, and high-purity argon is introduced into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are reversely rotated, the rotating speed is 30rpm, and the crystal growth speed is controlled to be 10 mm/h; obtained after the second zone melting (La)0.1Ce0.5Pr0.1Nd0.1Gd0.2)B6A single crystal.
Obtained in this example (La)0.1Ce0.5Pr0.1Nd0.1Gd0.2)B6Surface of single crystalThe crystal is smooth, and no trace of gas and impurity overflow appears, which indicates that the crystal growth is uniform. The crystal diameter is about phi 6.5mm and the length is 25 mm.
From the analysis of the sample by Laue diffraction and single crystal X-ray diffraction, the sample obtained in this example was a high quality single crystal.
Example 4
This example was prepared as follows (La)0.2Ce0.5Pr0.2Nd0.05Gd0.05) Single crystal:
(1) mixing LaB6、CeB6、PrB6、NdB6And GdB6Powder is prepared by mixing the following components in an atomic ratio of 4: 10: 4: 1: 1, ball-milling and uniformly mixing, putting into a graphite mold, then putting the graphite mold into a cavity of a discharge plasma sintering furnace, sintering under the condition that the vacuum degree is not higher than 6Pa, and setting technological parameters as follows: the sintering temperature is 1600 ℃, the sintering pressure is 40MPa, the heat preservation time is 5min, and the heating rate is 80 ℃/min; cooling to room temperature along with the furnace after sintering is finished, and taking out to obtain a polycrystalline sample;
(2) cutting a polycrystalline sample into polycrystalline rods with the diameter of 6mm, respectively taking the two polycrystalline rods as a material rod and a seed crystal, adding the polycrystalline rods into an optical zone melting furnace for zone melting for the first time, and introducing high-purity argon into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are reversely rotated, the rotating speed is 15rpm, and the crystal growth speed is controlled to be 20 mm/h;
(3) taking a product of primary zone melting as a material rod and LaB6The single crystal is used as seed crystal, added into an optical zone melting furnace for secondary zone melting, and high-purity argon is introduced into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are reversely rotated, the rotating speed is 30rpm, and the crystal growth speed is controlled to be 20 mm/h; obtained after the second zone melting (La)0.2Ce0.5Pr0.2Nd0.05Gd0.05)B6A single crystal.
Obtained in this example (La)0.2Ce0.5Pr0.2Nd0.05Gd0.05)B6The surface of the single crystal body is smooth, and no trace of gas and impurity overflow appears, which indicates that the crystal growth is uniform. The crystal diameter is about phi 6mm and the length is 30 mm.
From the analysis of the sample by Laue diffraction and single crystal X-ray diffraction, the sample obtained in this example was a high quality single crystal.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (1)

1. A preparation method of a large-size hexabasic rare earth boride single crystal cathode material is characterized by comprising the following steps of: the composition of the single crystal cathode material is (La)xCeyPrzNduGdv)B6Wherein x + y + z + u + v ═ 1;
the preparation method of the single crystal cathode material comprises the following steps:
(1) mixing LaB6、CeB6、PrB6、NdB6And GdB6The powder is mixed according to a molar ratio x: y: z: u: v, ball-milling and uniformly mixing, putting into a graphite mold, then putting the graphite mold into a cavity of a discharge plasma sintering furnace, sintering under the condition that the vacuum degree is not higher than 6Pa, and setting process parameters as follows: the sintering temperature is 1400-1850 ℃, the sintering pressure is 30-50 MPa, the heat preservation time is 5-15 min, and the heating rate is 60-200 ℃/min; cooling to room temperature along with the furnace after sintering is finished, and taking out to obtain a polycrystalline sample;
(2) cutting the polycrystalline sample into polycrystalline rods, respectively taking the two polycrystalline rods as a material rod and a seed crystal, adding the material rod and the seed crystal into an optical zone melting furnace for zone melting for the first time, and introducing high-purity argon into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are rotated reversely, the rotating speed is 15-30 rpm, and the crystal growth speed is controlled to be 10-40 mm/h;
(3) taking a product of primary zone melting as a material rod and LaB6Using single crystal as seed crystalAdding the mixture into an optical zone melting furnace for secondary zone melting, and introducing high-purity argon into the optical zone melting furnace; raising the power of the optical zone melting furnace until the seed crystal and the material rod are melted and a stable melting zone is formed; in order to make the melting zone more uniform, the material rod and the seed crystal are rotated reversely, the rotating speed is 15-30 rpm, and the crystal growth speed is controlled to be 1-20 mm/h; obtaining the large-size hexabasic rare earth boride single crystal cathode material after the secondary zone melting.
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CN108048907B (en) * 2017-12-14 2020-08-07 合肥工业大学 Preparation method of large-size and high-performance lanthanum hexaboride single crystal
CN109763170B (en) * 2019-03-25 2021-03-09 合肥工业大学 Preparation method of high-performance quaternary rare earth hexaboride-zirconium diboride composite material
CN115058775B (en) * 2022-06-07 2024-03-19 合肥工业大学 Large-size high-performance ternary rare earth composite single crystal material and preparation method thereof
CN114908422B (en) * 2022-06-29 2024-06-14 合肥工业大学 Strontium doped lanthanum hexaboride monocrystal and preparation method thereof

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* Cited by examiner, † Cited by third party
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US5238527A (en) * 1990-07-19 1993-08-24 National Institute For Research In Inorganic Materials Lanthanum boride type single crystal and method for growing the same
CN102808215A (en) * 2012-06-28 2012-12-05 北京工业大学 Preparation method of large-dimension multi-element rare earth boride (Ce0.9Pr0.1)B6 single crystal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238527A (en) * 1990-07-19 1993-08-24 National Institute For Research In Inorganic Materials Lanthanum boride type single crystal and method for growing the same
CN102808215A (en) * 2012-06-28 2012-12-05 北京工业大学 Preparation method of large-dimension multi-element rare earth boride (Ce0.9Pr0.1)B6 single crystal

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